Herbicidal indole sulfonamides

ABSTRACT

This invention relates to novel N-(heterocyclicaminocarbonyl) indole sulfonamides which are useful as agricultural chemicals and, in particular, as herbicides.

BACKGROUND OF THE INVENTION

This invention relates to novel N-(heterocyclicaminocarbonyl)indolesulfonamides which are useful as agricultural chemicals and, inparticular, as herbicidal agents.

Canadian Pat. No. 747,920 (issued Dec. 6, 1966, Upjohn) discloses3-(alkylcarbamoylsulfamoyl)-1-alkylindole-2-carboxylic acids and esters(i) as sedatives, diuretics, antifungal agents and/or sun screens##STR1## where R and R₂ are C₁ -C₄ alkyl, and

R₁ is H or C₁ -C₄ alkyl.

U.S. Pat. No. 4,127,405 teaches compounds which are useful forcontrolling weeds in wheat having the formula ##STR2## wherein R₁ is##STR3## R₃ and R₆ are independently hydrogen, fluorine, chlorine,bromine, iodine, alkyl of 1-4 carbon atoms, alkoxy of 1-4 carbon atoms,nitro, trifluoromethyl, cyano, CH₃ S(O)_(n) --or CH₃ CH₂ S(O)_(n) --;

R₄ is hydrogen, fluorine, chlorine, bromine or methyl;

R₅ is hydrogen, fluorine, chlorine, bromine, methyl or methoxy;

R₇ is hydrogen, fluorine, chlorine, bromine, alkyl of 1-2 carbon atomsor alkoxy of 1-2 carbon atoms;

R_(a) is hydrogen, methyl, chlorine or bromine;

R₉ and R₁₀ are independently hydrogen, methyl, chlorine or bromine;

W and Q are independently oxygen or sulfur;

n is 0, 1 or 2;

X is hydrogen, chlorine, bromine, methyl, ethyl, alkoxy of 1-3 carbonatoms, trifuloromethyl, CH₃ S-- or CH₃ OCH₂ --; and

Y is methyl or methoxy; or their agriculturally suitable salts; providedthat:

(a) when R₅ is other than hydrogen, at least one of R₃, R₄, R₆ and R₇ isother than hydrogen and at least two of R₃, R₄, R₆ and R₇ must behydrogen;

(b) when R₅ is hydrogen and all of R₃, R₄, R₆ and R₇ are other thanhydrogen, then all of R₃, R₄, R₆ and R₇ must be either chlorine ormethyl; and

(c) when R₃ and R₇ are both hydrogen, at least one of R₄, R₅ or R₆ mustbe hydrogen.

French Pat. No. 1,468,747 discloses the following para-substitutedphenylsulfonamides, useful as antidiabetic agents: ##STR4## wherein R═H,hydrogen, CF₃ or alkyl.

Logemann et al. Chem. Ab., 53, 18052 g (1959), disclose a number ofsulfonamides, including uracil derivatives and those having the formula:##STR5## wherein R is butyl, phenyl or ##STR6## and R₁ is hydrogen ormethyl. When tested for hypoglycemic effect in rats (oral doses of 25mg/100 g), the compounds in which R is butyl and phenyl were mostpotent. The others were of low potency or inactive.

Wojciechowski, J. Acta. Polon. Pharm. 19, p. 121-5 (1962) [Chem Ab., 591633 e] describes the syntthesis ofN-[(2,6-dimethoxypyrimidin-4-yl)aminocarbonyl]-4-methylbenzenesulfonamide:##STR7## Based upon similarity to a known compound, the author predictedhypoglycemic activity for the foregoing compound.

Netherlands Pat. No. 121,788, published Sept. 15, 1966, teaches thepreparation of compounds of Formula (i), and their use as general orselective herbicides, ##STR8## wherein R₁ and R₂ may independently bealkyl of 1-4 carbon atoms; and

R₃ and R₄ may independently be hydrogen, chlorine or alkyl of 1-4 carbonatoms.

Compounds of Formula (ii), and their use as antidiabetic agents, arereported in J. Drug. Res. 123 (1974), ##STR9## wherein R is pyridyl.

U.S. Patent application Ser. No. 244,172 discloses herbicidal compoundsof formulae ##STR10## wherein R₁ is H, C₁ -C₄ alkyl, NO₂, CN, C(O)CCl₃,SO₂ R₁₁, C(O)R₅ or CO₂ H;

R₂ is H or C₁ -C₄ alkyl;

R₃ is H, C₁ -C₄ alkyl, Cl or Br;

R₄ is H, C₁ 1-C₄ alkyl, cyanoethyl, C₅ -C₆ cycloalkyl, benzyl, phenylsubstituted with Cl or NO₂, or C(O)R₆ ;

R₅ is C₁ -C₄ alkyl or C₁ -C₄ alkoxy;

R₆ is C₁ -C₄ alkyl, or NR₇ R₈ ;

R₇ and R₈ are independently C₁ -C₂ alkyl;

R₉ is H, CH₃ or OCH₃ ;

R₁₁ is C₁ -C₄ alkyl;

R₁₀ is ##STR11## X is CH₃ or OCH₃ ; Y is H, CH₃, OCH₃,OCH₂ CH₃, OCH₂CF₃, Cl, CH₂ OCH₃, CH₂ OCH₂ CH₃ or CF₃ ;

Y¹ is H, CH₃, OCH₃, Cl or OCH₂ CH₃ ; and

Z is CH, N, CCH₃ CCH₂ CH₃, CCH₂ CH₂ Cl, CCl, CBr or CF;

and their agriculturally suitable salts.

The presence of undesired vegetation causes substantial damage to usefulcrops, especially agricultural products that satisfy man's basic foodand fiber needs, such as cotton, rice, corn, wheat, and the like. Thecurrent population explosion and concomitant world food and fibershortage demand improvements in the efficiency of producing these crops.Prevention or minimizing the loss of a portion of such valuable crops bykilling, or inhibiting the growth of undesired vegetation is one way ofimproving this efficiency. A wide variety of materials useful forkilling, or inhibiting (controlling) the growth of undesired vegetationis available; such materials are commonly referred to as herbicides. Theneed still exists however, for more effective herbicides.

SUMMARY OF THE INVENTION

This invention relates to novel compounds of Formula I and Formula II,suitable agricultural compositions containing them, and their method ofuse as general, as well as selective, pre-emergence or post-emergenceherbicides. ##STR12## where R is H, C₁ -C₄ alkyl, (CH₂)_(m) CO₂ R₉, CH₂OC₂ H₅, SO₂ R₁₀, CHO, SO₂ NR₁₁ R₁₂, CH₂ N(CH₃)₂ or CH₂ OCH₃ ;

R₁ is H, C₁ -C₄ alkyl, CO₂ R₆, C(O)NR₇ R₈, C(O)R₁₀,SO₂ R₁₀, or SO₂ NR₁₁R₁₂ ;

R₂ is H, C₁ -C₃ alkyl or SO₂ C₆ H₅ ;

R₃ is H, F, Cl, Br, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NO₂ ;

R₄ is H, Cl or Br;

R₅ is H or CH₃ ;

R₆ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, CH₂ CH₂ Cl or CH₂ CH₂ OCH₃ ;

R₇ and R₈ are independently H or C₁ -C₄ alkyl, provided that one totalnumber of carbon atoms is less than or equal to 4;

R₉ is H or C₁ -C₃ alkyl;

R₁₀ is C₁ -C₃ alkyl;

R₁₁ and R₁₂ are independently C₁ -C₃ alkyl, provided that the totalnumber of carbon atoms is less than or equal to 4.

m is 0, 1 or 2;

A is ##STR13## X is CH₃ or OCH₃ ; Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃, Cl,H, C₂ H₅ or N(CH₃)₂ ; and

Z is CH or N;

provided that

(1) when R₂ is SO₂ C₆ H₅, then R₁ and R are H or C₁ 14 C₄ alkyl.

(2) when Y is Cl, then Z is CH; and

(3) when m is 0, then R₉ is C₁ -C₃ alkyl.

PREFERRED COMPOUNDS

Preferred for reasons of higher herbicidal activity and/or morefavorable ease of synthesis are:

(1) Compounds of the generic scope of Formula I where R₁ is H, C₁ -C₃alkyl, CO₂ R₆, C(O)NR₇ R₈, SO₂ NR₁₁ R₁₂ or SO₂ R₁₀ ; and R₅ is H;

(2) Compounds of Preferred (1) where R₃ and R₄ are H;

(3) Compounds of Preferred (2) where R₂ is H or CH₃ ;

(4) Compounds of Preferred (3) where R₁ is H, CO₂ CH₃, SO₂ CH₃ or SO₂N(CH₃)₂ ;

(5) Compounds of Preferred (4) where Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃ orCl;

(6) Compounds of the generic scope of Formula II where R is H, C₁ -C₃alkyl, (CH₂)_(m) CO₂ R₉, SO₂ R₁₀ or SO₂ NR₁₁ R₁₂ ; and R₅ is H;

(7) Compounds of Preferred (6) where R₃ and R₄ are H;

(8) Compounds of Preferred (7) where R₂ is H or CH₃ ;

(9) Compounds of Preferred (8) where R is H, CH₃ or (CH₂)_(m) CO₂ --(C₁-C₃ alkyl); and

(10) Compounds of Preferred (9) where Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃or Cl.

Specifically Preferred for highest herbicidal activity and/or mostfavorable ease of synthesis are:

3-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylicacid, methyl ester;

3-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylicacid, methyl ester,

3-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylicacid, methyl ester,

3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylicacid, methyl ester;

3-[[(4,6-dimethyl-1,3,5-triazin-2-yl)aminocarbonyl]-aminosulfonyl]1-methyl-1H-indole-2-carboxylicacid, methyl ester;

3-[[(4-methyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]-1methyl-1H-indole-2-carboxylicacid, methyl ester;

N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

N-[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

N-[(4-methyl-6-methoxypyrimidin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)amniocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

N-[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

N-[(4-methyl-6-methoxy-1,3,5-triazin-2-yl)aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide;

3-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1H-indole-2-carboxylicacid, ethyl ester,

3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)aminocarbonyl]aminosulfonyl]-1H-indole-2-carboxylicacid, ethyl ester,

3-[[(4-methoxy-6-methyl-1,3,5-triazin-2yl)aminocarbonyl]aminosulfonyl]1H-indole-2-carboxylicacid, ethyl ester,

3-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1H-indole-2-carboxylicacid, ethyl ester,

3-[[(4,6-dimethylpyrimidin-2-yl)aminocarbonyl]aminosulfonyl]-1H-indole-2-carboxylicacid, ethyl ester,

DETAILED DESCRIPTION OF THE INVENTION

A general process for the preparation of compounds of Formula I isillustrated by the following equation: ##STR14##

More specifically, the compounds of this invention of Formula I areprepared by contacting a heterocyclilc amine of Formula V andchlorosulfonyl isocyanate to prepare the intermediate of Formula III.These compounds are preferably generated in situ and used withoutisolation in the synthesis of compounds of Formula I. The aminocarbonyl##STR15## sulfamoyl chloride of Formula III is then contacted with anindole of Formula IV, preferably in the presence of a Friedel-Craftscatlayst, to afford herbicidal indole sulfonamides of Formula I.

The heterocyclic amine of Formula V is dissolved or suspended in an artinert organic solvent, including but not limited to, dichloromethane,nitroethane, nitropropanes, tetrahydrofuran or nitroethane. The reactionmixture is maintained in an inert atmosphere at a temperature of -80° to0° C. When tetrahydrofuran is the solvent, the preferred temperaturerange is -80° to -50° C.; for nitromethane, the preferred range is -20°to 0° . One equivalent of chlorosulfonyl isocyanate, either neat or, iftetrahydrofuran is not the solvent, dissolved in the solvent, iscontacted with the amine at such a rate as to maintain the reactiontemperature within the preferred range. The reaction proceeds rapidlyand the reaction mixture is maintained within the preferred temperaturerange for a period of 0.1 to 1.0 hour to insure complete formation ofintermediate III. Compound III is then contacted at a temperature withinthe preferred range for the solvent employed with an equimolar amount ofindole IV, either neat or dissolved in the solvent.

From this point on, the reaction conditions employed depend on thenature of the substituents on the pyrrole ring of the indole nucleus.For reactions with indoles IV in which R₁ is H or C₁ -C₄ alkyl and R₂ isH or C₁ -C₃ alkyl, a Friedel-Crafts catalyst may optionally be added ata temperature within the preferred range. Friedel-Crafts catlaysts areextensively defined in Volume I, Chapter IV of "Friedel-Crafts andRelated Reactions", ed. G. A. Olah, Interscience Publ., New York, 1963.Preferred catalysts are those acidic halides, typified by aluminumchloride and bromide, which posses an electron deficient central metalatom capable of electron acceptance from basic reagents. More preferredis the use of aluminum (III) chloride in a catalytic quantity, the exactamount of which would be apparent to one skilled in the art. Thereaction mixture is allowed to warm to ambient temperature and ismaintained under an inert atmosphere until completion, usually for aperiod of from 0.5 to 24 hours. Tetrahydrofuran and nitroethane are thepreferred solvents for these reactions.

For reactions with indoles IV in which R₁ is other than H or C₁ -C₄alkyl or in which R₂ is SO₂ C₆ H₅, an equimolar amount of aFriedel-Crafts catalyst, preferably aluminum (III) chloride, is added tothe reaction mixture at this point. The reaction is allowed to warm toambient temperature and is then maintained under an inert atmosphere attemperatures ranging from ambient to the boiling point of the solventemployed, with nitromethane being the preferred solvent. The reactionproceeds to completion within 0.5 to 24 hours. In general, higherreaction temperatures and shorter reaction times (0.5 to 4 hours) affordthe highest yield. In all cases, the intermediate III is preferablyprepared in the same solvent in which the reaction with indole IV is tobe carried out.

The compounds of the invention of Formula I may be isolated bypartitioning the reaction mixture between dilute aqueous alkali and anorganic solvent such as dichloromethane or chloroform. The products aresoluble in the aqueous phase and may be precipitated from it afterseparation of the layers by the addition of a slight excess of an acidsuch as acetic acid or hydrochloric acid. If the products do notprecipitate on acidification they may be isolated by extraction into anorganic solvent such as dichloromethane, nitromethane or ethyl acetatefollowed by evaporation of the solvent. This procedure is most useful incases in which tetrahydrofuran is the reaction solvent.

When the reaction is carried out in a water-immiscible solvent such asdichloromethane or nitromethane, isolation of the products may best becarried out by contacting the reaction mixture with water, followed byseparation of the organic phase and further extraction of the productsinto an organic solvent such as dichloromethane, nitromethane,nitroethane or ethyl acetate. Evaporation of the organic solutionaffords the crude products of Formula I.

Purification of the reaction products may be accomplished by triturationwith an appropriate solvent, recrystallization or chromatography.

The procedures described generally by Equation 1 are preferred for thepreparation of indole sulfonamides of Formula I which R₁ is C₂ R₆,C(O)R₁₀, SO₂ R₁₀ or SO₂ NR₁₁ R₁₂ and R₂ is H or C₁ -C₃ alkly or in whichR₁ is H or C₁ -C₄ alkly and R₂ is C₁ -C₃ alkyl or SO₂ C₆ H₅. For casesin which R₁ is H, isomeric products of Formulae I and II (R═R₁ ═H) aregenerally obtained by these methods and may be separated by columnchronatography, preparative high pressure or medium pressurechromatography or similar methods.

Indole sulfonamides of Formula I in which R₁ is C(O)NR₇ R₈ arepreferably prepared from the corresponding compounds in which R₁ is CO₂CH₃ by reaction with dialkylaluminum-N-alklamide derivatives as shown inEquation 2. This method is ##STR16## disclosed in unexamined EuropeanPat. No. 7687, filed Feb. 6, 1980.

Indole sulfonamides of Formula I in which R₁ is H or C₁ -C₄ alkyl and R₂is H are preferably prepared by alkaline hydrolysis of the correspondingcompounds in which R₂ is SO₂ C₆ H₅ as shown by equation 3. The reactionis carried out in an excess of aqueous alkali, ##STR17## preferably inthe presence of a water-miscible co-solvent such as ethanol, dioxane ortetrahydrofuran at temperatures ranging from ambient to the refluxtemperature of the solvent mixture employed. After 1 to 24 hours, thereaction mixture is diluted with water and acidified, at 0°-5° withaqueous hydrochloric acid to precipitate the product.

The compounds of this invention of Formula II can be prepared by one ofthe two methods illustrated below in Equations 4 and 5. ##STR18##

As shown in Equation 4 compounds of Formula II, can be prepared byreacting an amino-hetero-cycle V with an appropriately substitutedsulfonyl isocyanate of Formula VI. The reaction is best carried out ininert, aprotic organic solvents such as acetonitrile, methylene chlorideor tetrahydrofuran at ambient temperature. The mode of addition is notcritical; however, it is often convenient to add a solution of thesulfonyl isocyanate VI to a stirred solution of amino-heterocycle V. Thereaction is generally exothermic. In some cases, the desired product isinsoluble in the reaction medium and crystallizes from it in pure form.Products soluble in the reaction medium are isolated by evaporated ofthe solvent, trituration of the residue with solvents such a1-chlorobutane, methylene chloride or ethyl ether, and filtration.

The intermediate sulfonyl isocyanates of formula VI are prepared byreacting the corresponding sulfonamides of Formula VII with phosgene andn-butyl isocyanate at reflux in a solvent such as xylenes and in thepresence of a catalytic amount of a non-nucleophic base such as1,4-diazabicyclo(2,2,2)octane. Useful procedures are reported by H.Ulrich and A. A. Y. Sayigh, Newer Methods of Preparative OrganicChemistry, Vol. VI. pp. 223-241, Academic Press, New York, W. Foerst,Ed.

Compounds of Formula II can also be prepared as shown in Equation 5 byreaction of a sulfonamide of Formula VII with an appropriate methylcarbamate of Formula VIII in the presence of trimethylaluminum. Morespecifically, the reaction mixture containing sulfonamide VII and aninert, aprotic solvent such as methylene chloride or toluene is reactedunder an inert atmosphere with trimethylaluminum and the resultingmixture stirred at ambient temperature until gas evolution ceases. Themethyl carbamate VIII is added, generally neat, and the reaction isallowed to proceed at temperatures ranging from ambient to reflux for 16to 96 hours. The product can be isolated after addition of aqueoushydrochloric acid to the reaction mixture followed by the partitioningof the product into methylene chloride. The product may be purified bycrystallization form solvents such as 1-chlorobutane, ethyl ether ormethylene chloride or by chromatography.

Either of the methods shown by Equations 4 and 5 is suitable for thepreparation of compounds of Formula II in which R is H, C₁ -C₄ alkyl,SO₂ R₁₀, SO₂ NR₁₁ R₁₂, CH₂ N(CH₃)₂, CH₂ OCH₂ CH₃ or CH₂ OCH₃ and R₂ isC₁ -C₃ alkyl or SO₂ C₆ H₅. The method of Equation 4 is more preferredfor preparation of Compounds II with the above listed values of R whereR₂ is H. This method is also preferred for preparation of Compounds IIin which R is (CH₂)_(m) CO₂ R₉, R₉ is other than H and R₂ is H or C₁ -C₃alkyl.

Compounds of Formula II in which R is (CH₂)_(m) CO₂ R₉, R₉ is H and R₂is H or C₁ -C₃ alkyl may best be prepared from the correspondingcompounds in which R₉ is C₁ -C₃ alkyl by alkaline hydrolysis. Compoundsof Formula II in which R is CHO may be prepared from the correspondingcompounds in which R is (CH₂)_(m) CO₂ R₉, m is O and R₉ is CH₃ (CompoundIX) by partial reduction with a reducing agent ##STR19## such asdiisobutylaluminum hydride. Procedures for these conversions would beapparent to one skilled in the art.

PREPARATION OF REACTANTS

The synthesis of heterocyclic amine derivatives such as those of FormulaV has been reviewed in "The Chemistry of Heterocyclic Compounds", aseries published by Interscience publ., New York and London.2-Amino-pyrimidines are described by D. J. Brown in "The Pyrimidines",Vol. XVI of the above series. 2-Amino-1,3,5-triazins are reviewed by E.M. Smolin and L. Rapoport in "s-Triazines and Derivatives," Vol. XIII ofthe same series. The synthesis of triazines of triazines is alsodescribed by F. C. Schaeffer, U.S. 3,154,547 and by K. R. Huffman and F.C. Schaeffer, J. Org. Chem., 28, 1812-1821 (1963).

The heterocyclic amines of Formula V in which R₅ is CH₃ may be preparedby the following procedure, or by modifications thereof apparent to oneskilled in the art. ##STR20##

A solution of the amine X in concentrated hydrochloric acid is reactedwith an aqueous sodium nitrite solution and the chloro compound XI isisolated in the usual manner by filtration of the acidic solution (seefor example, Bee and Rose, J. Chem. Soc. C., 2051 (1966) for the case inwhich Z is CH and X and Y are OCH₃). Displacement of the chlorine may beaccomplished by heating with an excess of methylamine in water to obtainthe methylaminoheterocycle XII.

Pyrimidinyl and triazinyl methy carbamates of Formula VIII may beprepared by the method illustrated in Equation 6. A heterocyclic amineof Formula V is reacted with one or two equivalents of sodium hydride,when R₅ is CH₃ or H, respectively, ##STR21## and excess dimethylcarbonate to form VIII.

This reaction takes place in an inert solvent such as tetrehydrofuran at25° to 70° C. for 1 to 24 hours. The product is isolated by (a) additionof two equivalents of concentrated hydrochloric acid and aqueoussaturated sodium chloride and (b) separation of the organic phasefollowed by concentration to dryness in vacuo.

The preperation of indole derivatives has been extensively reviewed in"Indoles", Parts One-Four, Vol. XXV of the series "The Chemistry ofHeterocyclic Compounds" and in "The Chemistry of Indoles", by R. J.Sundberg, Academic Press, New York and London (1970). Two otherparticularly useful procedures are described by P. G. Gassman in U.S.Pat. No. 3,901,899 and U.S. Pat. No. 3,960,926.

Indoles of Formula IV in which R₁ is H, C₁ -C₄ alkyl or CO₂ R₆ and R₂ isH or C₁ -C₃ alkyl are well-known in the literature. Indoles of FormulaIV in which R₁ is H or C₁ -C₄ alkyl and R₂ is SO₂ C₆ H₅ are preparedfrom the corresponding compounds in which R₂ is H by reaction with oneequivalent of a base, such as sodium methylsulfonylmethide orn-butyllithium, in ether or tetrahydrofuran, followed by reaction withphenylsulfonyl chloride (see, for example, Sundberg and Russell, J. Org.Chem. 38, 3324 (1973) and Saulnier and Gribble, J. Org. Chem. 47, 747(1982)).

Indoles of Formula IV in which R₁ is COR₁₀, may be prepared via themethod of Equation 7. Reaction of N-phenylsulfonyl indoles of FormulaXIII in tetrahydrofuran ##STR22## with a slight excess of lithiumdiisopropylamine (LDA) at low temperature, followed by warming toambient temperature, recooling and quenching the anion thus formed withan acid chlorid R₁₀ COCl results in the formation of compounds ofFormula XIV (see, for example, Saulnier and Gribble, ibid.

Indoles of Formula IV in which R₁ is SO₂ R₁₀ may be prepared asillustrated by Equation 8. ##STR23## Lithiation of XIII as describedabove followed by quenching with a dialkyl disulfide (R₁₀ S)₂ affordsN-phenylsulfonyl-2-alkylthioindoles which may be oxidized to alkylsulfonyl indoles of Formula XV by methods described by Wieland, et. al.,Justus Liebigs Ann. Chem. 713, 186 (1968) and Hino, et. al., J. Chem.Soc., Sect. D 473 (1972).

Equation (9) represents a method of preparation for indoles of FormulaIV in which R₁ is SO₂ NR₁₁ R₁₂. Lithiation in this method is carried outunder an inert ##STR24## atmosphere by the slow addition of an ethersolution of XIII to 1.1 equivalents of LDA at 0° followed by stirring at0° for 0.5 to 2 hours. The resulting slurry is added to a solution of 2equivalents of sulfonyl chloride in an equal volume of hexanes at -20 °to -30°. After 0.5 to 1 hour at -20° to -30°, the reaction mixture isallowed to warm to ambient temperature, stirred until completion(generally 2 to 8 hours), then diluted with water. TheN-phenylsulfonyl-2-chlorosulfonyl indoles are isolated by extractioninto ethyl acetate and purified by trituration with ether or similarsolvents. Reaction of these products with an excess of amine HNR₁₁ R₁₂using procedures that would be obvious to one skilled in the art affordsindole sulfonamides XVI.

Indoles of Formula IV in which R₁ is COR₁₀, SO₂ R₁₀ or SO₂ NR₁₁ R₁₂ andR₂ is H are prepared from the corresponding indoles in which R₂ is SO₂C₆ H₅ (compounds XIV, XV and XVI respectively) by alkaline hydrolysis,according to the procedures of Equation 3. In cases in which the productdoes not precipitate upon acidification, it may be isolated byextraction into ethyl acetate or ether. Alkylation of these indoles ornitrogen by procedures well-known in the literature affords compounds ofFormula IV in which R₁ is COR₁₀, SO₂ R₁₀ or SO₂ NR₁₁ R₁₂ and R₂ is C₁-C₃ alkyl.

Indole-2-sulfonamides of Formula VII in which R is H, C₁ -C₄ alkyl, CH₂OCH₃ or CH₂ OCH₂ CH₃ and R₂ is SO₂ C₆ H₅ may be prepared by the methodof Equation 10 according to the procedures of Equation 9. Thecorresponding compounds of Formula VII in which R₂ is H may be preparedby alkaline hydrolysis of XVII according ##STR25## to the procedures ofEquation 3. Preparation of the corresponding compounds in which R₂ is C₁-C₃ alkyl may be carried out by the method illustrated below. ##STR26##The protected indole-2-sulfonamide of Formula XVIII in which R is H, C₁-C₄ alkyl, CH₂ OCH₃ or CH₂ OCH₂ CH₃ is prepared by the method ofEquation 9. Alkaline hydrolysis as described above affords XIX which maybe alkylated on the more nucleophilic indole nitrogen after dianionformation by procedures which would be known to one skilled in the art.The t-butyl protecting group is then removed with trifluoroacetic acidto afford the desired indole-2-sulfonamides in which R₂ is C₁ -C₃ alkyl.

Lithiation of protected indole-2-sulfonamides of Formula XVIII in whichR is H (compound XX) provides access to compound of Formula VII in whichR is SO₂ R₁₀ or (CH₂)_(m) CO₂ R₉ and m is 0 or 1. Reaction of indole XXunder an inert atmosphere with 2 equivalents of n-butyl lithium in etheror tetrahydrofuran at -20° to 0°, optionally in the presence oftetraethylenediamine, affords the 3-lithio derivative. ##STR27##Quenching this anion with A C₁ -C₃ alkyl chloroformate, a C₁ -C₃ alkyl αbromoacetate or a C₁ -C₃ dialkyl disulfide, followed in the last case byoxidation, affords indole-2-sulfonamides of Formula XVIII in which R is(CH₂)₀ CO₂ R₉, (CH₂)₁ CO₂ R₉ or SO₂ R₁₀ respectively. Suitableprocedures for these conversions would be known to one skilled in theart. Indole-2-sulfonamides of Formula VII in which R₂ is H or C₁ -C₃alkyl, R is SO₂ R₁₀ or (CH₂)_(m) CO₂ R₉ and m is 0 or 1 may then beprepared, using procedures already described or well-known in theliterature, by alkaline hydrolysis of the N-phenylsulfonyl group,re-esterification when R is (CH₂)_(m) CO₂ R₉, N-alkylation if desired,and removal of the t-butyl protecting group.

Indoles of Formula VII in which R is SO₂ NR₁₁ R₁₂ are prepared from thecorresponding compounds of Formula XXI, obtained by alkaline hydrolysisof XX, by the procedure shown in Equation 12. Reaction of XXI ##STR28##with thionyl chloride affords the indole-3-sulfonyl chloride, which isconverted to the sulfonamide and oxidized to the sulfonamide usingprocedures described by J. Szmuszkovicz in Canadian Pat. No. 747,920 andin J. Org. Chem. 29, 179 (1964). Optional alkylatin of the indolenitrogen followed by trifluoracetic acid hydrolysis as described aboveafford indoles VII in which R is SO₂ NR₁₁ R₁₂ and R₂ is H or C₁ -C₃alkyl.

Reaction of indole XXI with acrylic acid in the presence of acetic acidaffords the indole-3-propionic acid. Esterification, alkylation of theindole nitrogen, if desired, and trifluoroacetic acid hydrolysis givesrise to indoles of Formula VII in which R is (CH₂)_(m) CO₂ R₉, m is 2and R₂ is H or C₁ -C₃ alkyl. ##STR29##

Reaction of indole XXI with formaldehyde and dimethylamine under Mannichreaction conditions followed by optional alkylation of the indolenitrogen and removal of the t-butyl protecting group affords indoles ofFormula VII in which R is CH₂ N(CH₃)₂ and R₂ is H or C₁ -C₃ alkyl.

Agriculturally suitable salts of Formula I and II are also usefulherbicides and can be prepared by a number of ways known to the art.

The compounds of the invention and their preparation are furtherillustrated by the following samples. Unless otherwise indicated, allparts are by weight and all temperatures are in °C.

EXAMPLE 1 Preparation of Methyl3-[[(4,6-dimethylpyrimidin-2-yl)-aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylate.

To a stirred suspension of 2.59 g (0.021 mole) of2-amino-4,6-dimethylpyrimidine in 75 ml dry nitromethane at -10° wasadded dropwise under nitrogen via syringe 2.0 ml (0.023 mole) ofchlorosulfonyl isocyanate at such a rate as to maintain the temperaturebelow 0°. The resulting clear solution was stirred for 0.5 hour at -5°to -10° and then contacted dropwise with a solution of 3.97 g (0.021mole) of methyl 1-methyl-1H-indole-2-carboxylate dissolved in 40 ml ofdry nitromethane. Upon completion of the addition, 2.95 g (0.022 mole)of aluminum (III) chloride was added in one portion. The reactionmixture was stirred at reflux for 3 hours, then cooled to roomtemperature and poured into 300 ml H₂ O. Methylene chloride was addedand the layers separated. The aqueous solution was extracted with twoadditional portions of CH₂ Cl₂ and the combined organic solutions werewashed with H₂ O, dried over MgSO₄ and evaporated in vacuo. Triturationof the residue with minimal CH₂ Cl₂ afforded 2.02 g of the desiredproduct as a white solid, m.p. 212°-215° (d). The infrared spectrum ofthe product included absorptions at 3215 and 3150 (NH), 1730 (C═O), 1710(C═O), 1345 and 1150 (SO₂) cm⁻¹, 'H NMR (CDCl₃ /DMSO-d₆)δ 2.43 (s, 6H,pyrimidine CH₃), 3.88 (s, 6H, ester CH₃ and N--CH₃), 6.90 (s, 1H,pyrimidine CH), 7.23-7.75 (m, 3H, indole CH), 8.16-8.47 (m, 1H, indoleCH), 10.30 (s, 1H, NH), 13.26 (br s, 1H, NH). Mass spectral analysisshowed m/e 123, ##STR30##

EXAMPLE 2 Preparation of Methyl3-[[(4-methoxy-6-methyl-pyrimidine-2-yl)aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylate.

To a stirred suspension of 2.92 g (0.021 mole) of2-amino-4-methoxy-6-methylpyrimidine in 75 ml dry CH₃ NO₂ at -10° wasadded dropwise under nitrogen via syringe 2.0 ml (0.023 mole) ofchlorosulfonyl isocyanate at such a rate as to maintain the temperaturebelow 0°. The resulting clear solution was stirred 0.5 hour at -5° to-10° and then contacted dropwise with a solution of 3.97 g (0.021 mole)of methyl 1-methyl-1H-indole-2-carboxylate dissolved in 25 ml of drynitromethane. Upon completion of the addition, 2.95 g (0.022 mole) ofaluminum (III) chloride was added in one portion. The reaction mixturewas stirred at reflux for 3 hours, then cooled to room temperature andpoured into 300 ml H₂ O. Dichloromethane was added and the layers wereseparated. The aqueous solution was extracted with two additionalportions of CH₄ Cl₂ and the combined organic solutions washed with H₂ O,dried over MgSO₄ and evaporated in vacuo. Chromatography on silica gelwith 5% acetone in CH₂ Cl₂ afforded 1.63 g of the desired product as awhite solid, m.p. 200°-203° (d). The infrared spectrum of the productincluded absorptions at 3190 (NH), 1715 (C═O), 1703 (C═O), 1340 and 1150(SO₂) cm⁻¹, 'H NMR (CDCl₃ /DMSO-d₆) δ2.45 (s, 3H, pyrimidine CH₃), 3.95(s, 3H, OCH₃), 4.0 (s, 6H, OCH₃ N--CH₃), 6.37 (s, 1H, pyrimidine CH),7.23-7.56 (m, 3H, indole CH), 8.18-8.47 (m, 1H, indole CH), 9.50 (s, 1H,NH), 13.08 (br s, 1H, NH). Mass spectral analysis showed m/e 139,##STR31##

EXAMPLE 3 Preparation of 1-phenylsulfonyl-1H-indole-2-sulfonyl chloride

To a stirred solution of lithium diisopropylamine (prepared from 0.124mole diisopropylamine in 50 ml ether and 82 ml of 1.6M n-butyllithium inhexanes) at 0° was added dropwise under nitrogen over 40 minutes asolution of 29.2 g (0.1135 mole) of 1-phenylsulfonyl-1H-indole in 400 mldry ether. The resulting slurry was stirred 30 minutes at 0°, thentransferred via canula to a solution of 18.3 ml (0.227 mole) of sulfurylchloride in 400 ml hexanes at -20° to -30° (dry ice/CCl₄ bath). Near theend of the addition there was a gradual 5° exotherm. After 30 min.additional cooling, the ice bath was removed and stirring continued for4 hours at ambient temperature. The slurry was poured into water andethyl acetate was added with stirring until all solids dissolved. Thelayers were separated and the aqueous phase extracted 2 times with ethylacetate. The combined organic solutions were washed with water, driedover MgSO₄ and evaporated in vacuo to a dark semisolid. Ethertrituration afforded 25.07 g of tan solid, m.p. 118°-120° and a secondcrop of 3.60 g tan solid, m.p. 115°-118°. ¹ H NMR (CDCl₃) δ7.17-7.84 (m,7H), 8.03-8.21 (m, 2H), 8.36 (d, 1H, J=9 hz, C-3 proton). The infraredspectrum of the product included absorptions at 1385, 1180 and 1185 cm⁻¹for sulfonyl chloride.

EXAMPLE 4 Preparation of 1-phenylsulfonyl-1H-indole-2-sulfonamide

To a stirred solution of 10 g (0.0281 mole) of1-phenylsulfonyl-1H-indole-2-sulfonyl chloride in 150 ml anhydrous THFwas added at -78° 4 ml (0.192 mole) of anhydrous ammonia. The resultingslurry was allowed to warm to room temperature over 30 minutes, then wassparged with nitrogen to remove excess ammonia. The slurry was filteredand the filtrate evaporated in vacuo to afford 9.19 g of tan solid, m.p.199°-200.5°, ¹ H NMR (CDCl₃ /DMSO-d₆) δ7.23-7.77 (m, 9H), 8.1-8.28 (m,3H, C-3 proton and SO₂ NH₂). The infrared spectrum of the productincluded absorptions at 3400 and 3280 cm⁻¹ (SO₂ NH₂).

EXAMPLE 5 Preparation of 1H-indole-2-sulfonamide

To a stirred solution of 2.4 g (7.13 mmol) of1-phenylsulfonyl-1H-indole-2-sulfonamide in 50 ml THF was added 0.86 g(21 mmol) of sodium hydroxide dissolved in 5 ml H₂ O. The mixture wasrefluxed for 5 hours, then cooled to room temperature, poured into waterand acidified slightly with 1N HCl. This solution was extracted 2 timeswith ethyl acetate and the combined organic layers were dried over MgSO₄and evaporated in vacuo to afford 0.58 g of a pale tan solid, m.p.190°-192° ¹ H NMR (CDCl₃ /DMSO-d₆) δ6.92-7.72 (m, 7H), 11.59 (br, 1H,indole NH). The infrared spectrum of the product included absorptions at3385, 3280, 1310 and 1140 (SO₂ NH₂) and at 3340 cm⁻¹ (indole NH).

EXAMPLE 6 Preparation of N-[(4.6-dimethylpyrimidin-2-yl)aminocarbonyl]-1H-indole-2-sulfonamide.

A mixture of 5.0 g (0.0255 mole) of 1H-indole-2-sulfonamide, 2.9 ml(0.0255 mole) of n-butylisocyanate, a catalytic amount of1,4-diazabicyclo[2,2,2] octane and 75 ml of xylenes was heated undernitrogen to 138°. Phosgene was condensed into the reaction mixture untilthe temperature fell to 130°. As phosgene was consumed, the temperaturegradually increased to 138°. Further additions of phosgene were madeuntil the reaction temperature failed to return to 138°. Unreactedphosgene was removed with a nitrogen stream (2N NaOH trap) and heatingwas continued for 15 minutes. The reaction mixture was cooled to roomtemperature, filtered under nitrogen and evaporated in vacuo to affordthe sulfonylisocyanate intermediate which was used without purificationin the second step of the reaction.

A solution of 1.0 g (4.47 mmol) of the above isocyanate in 5 ml dryacetonitrile was added under nitrogen to a mixture of 0.5 g (4.06 mmol)of 2-amino-4.6-dimethylpyrimidine in 5 ml dry acetonitrile and themixture allowed to stir overnight at ambient temperature. Theprecipitate was collected by filtration and washed with ether to affordthe desired material.

EXAMPLE 7 Preparation of N-[(4.6-dimethylpyrimidin-2-yl)aminocarbonyl]-1-phenysulfonyl-1H-indole-2-sulfonamide

To a slurry of 1.0 g (3.0 mmol) 1-phenylsulfonyl-1H-indole-2-sulfonamidein 20 ml methylene chloride was added under nitrogen at ambienttemperature 1.65 ml (3.3 mmol) of a 2M trimethylaluminum solution intoluene. The resulting mixture was stirred until gas evolution hadceased, then 0.54 g (3 mmol) of methyl (4.6-dimethylpyrimidin-2-yl)carbamate was added in one portion. The mixture was stirred at refluxovernight, then cooled to room temperature, poured into 50 ml ofice-cold 5% HCl and stirred 5 minutes. The layers were separated and theaqueous phase extracted 2 times with ethyl acetate. The combined organiclayers were washed with H₂ O, dried over MgSO₄ and evaporated in vacuoto afford the desired product.

By using methods described generally above and illustrated in Examples 1through 7, compounds as shown in the following tables can similarly beprepared. These tables are not meant to be all inclusive but onlyillustrative of the breadth of the invention.

                                      TABLE I                                     __________________________________________________________________________     ##STR32##                                                                    R.sub.1    R.sub.2                                                                             R.sub.3                                                                             R.sub.4                                                                           R.sub.5                                                                           X   Y      Z   m.p. (°C.)               __________________________________________________________________________    H          H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  H          H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  H          CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   H          C.sub.3 H.sub.7                                                                     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  H          C.sub.2 H.sub.5                                                                     5-NO.sub.2                                                                          H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   N                                   H          H     H     6-Cl                                                                              H   OCH.sub. 3                                                                        Cl     CH                                  H          H     H     H   H   OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                    CH                                  H          SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  H          SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   H          SO.sub.2 C.sub.6 H.sub.5                                                            5-Cl  7-Cl                                                                              H   CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                   CH                                  H          SO.sub.2 C.sub.6 H.sub.5                                                            6-CH.sub.3                                                                          H   CH.sub.3                                                                          CH.sub.3                                                                          H      CH                                  CH.sub.3   H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CH.sub.3   H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CH.sub.3   H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   CH.sub.3   H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CH.sub.3   H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CH.sub.3   CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CH.sub.3   CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CH.sub.3   CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CH.sub.3   CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CH.sub.3   C.sub.2 H.sub.5                                                                     5-Cl  H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   C.sub.2 H.sub.5                                                                          H     6-OCH.sub.3                                                                         H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   C.sub.2 H.sub.5                                                                          H     H     H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                  n-C.sub.4 H.sub.9                                                                        H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   s-C.sub.4 H.sub.9                                                                        H     7-C.sub.2 H.sub.5                                                                   H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  i-C.sub.3 H.sub.7                                                                        H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   i-C.sub.3 H.sub.7                                                                        H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                             N                                   i-C.sub.3 H.sub.7                                                                        H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  i-C.sub.3 H.sub.7                                                                        H     4-OC.sub.3 H.sub.7                                                                  H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  i-C.sub.3 H.sub.7                                                                        H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  i-C.sub.3 H.sub.7                                                                        CH.sub. 3                                                                           H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   i-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                   H     7-Br                                                                              H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   N                                   CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH  212-215(d)                      CO.sub.2 CH.sub.3                                                                        C.sub.2 H.sub.5                                                                     7-Cl  5-Cl                                                                              H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                  CO.sub.2 CH.sub.3                                                                        C.sub.2 H.sub.5                                                                     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CO.sub.2 CH.sub.3                                                                        C.sub.3 H.sub.7                                                                     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CO.sub.2 CH.sub.3                                                                        C.sub.3 H.sub.7                                                                     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N   205-207                         CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH  143-145(d)                      CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH  134-138(d)                      CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N   165-169(d)                      CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH  197-201                         CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                    CH                                  CO.sub.2 C.sub.2 H.sub.5                                                                 H     5-OC.sub.2 H.sub.5                                                                  H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CO.sub.2 C.sub.2 H.sub.5                                                                 H     5-C.sub.2 H.sub.5                                                                   H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH  123-217(d)                      CO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     4-Br                                                                              H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   CO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                   ##STR33## H     4-F   H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                    ##STR34## H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                   ##STR35## H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                   ##STR36## H     6-OC.sub.2 H.sub.5                                                                  H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                    ##STR37## H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR38## H     6-Br  H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                    ##STR39## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                    ##STR40## H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                   ##STR41## H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR42## CH.sub.3                                                                            H     6-Br                                                                              CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                             N                                    ##STR43## CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                   ##STR44## CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                    ##STR45## C.sub.2 H.sub.5                                                                     5-CH.sub.3                                                                          H   H   OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                     N                                    ##STR46## i-C.sub.3 H.sub.7                                                                   7-C.sub.3 H.sub.7                                                                   H   H   OCH.sub.3                                                                         H      N                                    ##STR47## H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                    ##STR48## H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                   ##STR49## H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                    ##STR50## H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                   ##STR51## H     5-Br  H   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.2 CH.sub.3                                                                    N                                    ##STR52## H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR53## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                    ##STR54## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                   ##STR55## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                    ##STR56## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR57## CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                   ##STR58## CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub. 2 CH.sub.3                                                                  N                                    ##STR59## C.sub.3 H.sub.7                                                                     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                    ##STR60## i-C.sub.3 H.sub.7                                                                   H     H   CH.sub.3                                                                          OCH.sub.3                                                                         Cl     CH                                   ##STR61## C.sub.2 H.sub.5                                                                     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                    ##STR62## H     4-OCH.sub.3                                                                         H   H   OCH.sub.3                                                                         CH.sub.2 CH.sub.3                                                                    CH                                   ##STR63## H     6-NO.sub.2                                                                          H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR64## CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                  CO.sub.2 .sub.-t-C.sub.4 H.sub.9                                                         H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   CO.sub.2 -n-C.sub.4 H.sub.9                                                              H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CO.sub.2 .sub.-s-C.sub.4 H.sub.9                                                         H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CO.sub.2 (CH.sub.2).sub.2 Cl                                                             H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CO.sub.2 (CH.sub.2).sub.2 Cl                                                             H     4-C.sub.2 H.sub.5                                                                   H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CO.sub.2 (CH.sub.2).sub.2 Cl                                                             CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH                                  CO.sub.2 (CH.sub.2).sub.2 Cl                                                             H     H     H   CH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CO.sub.2 (CH.sub.2).sub.2 Cl                                                             H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      H     H     H   H   CH.sub.3                                                                          Cl     CH                                  CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                   N                                   CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      H     7-OC.sub.3 H.sub.7                                                                  H   H   OCH.sub.3                                                                         H      CH                                  CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      i-C.sub.3 H.sub.7                                                                   H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CO.sub.2 (CH.sub.2).sub.2 OCH.sub.3                                                      H     H     H   H   OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                    N                                   CON(CH.sub.3).sub.2                                                                      H     H     6-Br                                                                              H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CON(CH.sub.3).sub.2                                                                      H     7-F   H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   CON(CH.sub.3).sub.2                                                                      H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CON(CH.sub.3).sub.2                                                                      H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CON(CH.sub.3).sub.2                                                                      H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   CON(CH.sub.3).sub.2                                                                      H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         H      CH                                  CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            6-OCH.sub.3                                                                         H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CON(CH.sub.3).sub.2                                                                      CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   CON(CH.sub.3).sub.2                                                                      C.sub.2 H.sub.5                                                                     H     H   H   CH.sub.3                                                                          OCH.sub.2 CH.sub.3                                                                   N                                   CON(CH.sub.3).sub.2                                                                      i-C.sub.3 H.sub.7                                                                   H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   CON(CH.sub.3).sub.2                                                                      C.sub.3 H.sub.7                                                                     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CONHCH.sub.3                                                                             H     H     H   H   CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                    CH                                  CONHCH.sub.3                                                                             H     H     7-Cl                                                                              CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CONHC.sub.2 H.sub.5                                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CONHC.sub.2 H.sub.5                                                                      CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                   CH                                  CON(CH.sub.3)C.sub.2 H.sub.5                                                             CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CON(CH.sub.3)C.sub.2 H.sub.5                                                             H     5-F   H   H   OCH.sub.3                                                                         CH.sub.2 CH.sub.3                                                                    N                                   CONHC.sub.3 H.sub.7                                                                      H     H     H   H   CH.sub.3                                                                          Cl     CH                                  CONH .sub.-t-C.sub.4 H.sub.9                                                             H     5-OC.sub.3 H.sub.7                                                                  H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CON(CH.sub.3)C.sub.3 H.sub.7                                                             H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   CONH .sub.-i-C.sub.4 H.sub.9                                                             H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  CONH .sub.-i-C.sub.3 H.sub.7                                                             H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   COCH.sub.3 H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  COCH.sub.3 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   COC.sub.2 H.sub.5                                                                        H     H     H   CH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                            N                                   COC.sub. 2 H.sub.5                                                                       H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  COC.sub.2 H.sub.5                                                                        H     H     H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                  COC.sub.3 H.sub.7                                                                        H     6-NO.sub.2                                                                          H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   COC.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                   4-Br  H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   COC.sub.3 H.sub.7                                                                        H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   COi-C.sub.3 H.sub.7                                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  COi-C.sub.3 H.sub.7                                                                      H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 CH.sub.3                                                                        H     7-OC.sub.2 H.sub.5                                                                  H   CH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            5-OCH.sub.3                                                                         H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      CH                                  SO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH                                  SO.sub.2 CH.sub.3                                                                        H     4-Cl  6-Cl                                                                              H   CH.sub.3                                                                          Cl     CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            4-Cl  H   H   CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                    CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            4-Cl  H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            4-Cl  H   H   OCH.sub.3                                                                         Cl     CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   CH.sub.3                                                                          OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 H     H     6-Br                                                                              H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 H     7-Br  H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.2 H.sub.5                                                                 C.sub.3 H.sub.7                                                                     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 H     4-Cl  H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            H     H   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            5-OCH.sub.3                                                                         H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 C.sub.3 H.sub.7                                                                 CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 C.sub.2 H.sub.5                                                                     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 C.sub.3 H.sub.7                                                                 i-C.sub.3 H.sub.7                                                                   4-NO.sub.2                                                                          H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 N(CH.sub.3).sub. 2                                                              H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.3).sub.2                                                               H     H     H   CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                                                                      N                                   SO.sub.2 N(CH.sub.3).sub.2                                                               H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               H     5-Cl  7-Cl                                                                              H   CH.sub.3                                                                          Cl     CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                     CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               C.sub.2 H.sub.5                                                                     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               C.sub.3 H.sub.7                                                                     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH                                  SO.sub.2 N(CH.sub.3).sub.2                                                               H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H     6-Cl  H   H   OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                    N                                   SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H     6-Cl  H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 N(CH.sub.3 )C.sub.2 H.sub.5                                                     H     6-Cl  H   CH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                            N                                   SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H     6-Cl  H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      CH.sub.3                                                                            5-C.sub.2 H.sub.5                                                                   H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                   CH                                  SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      CH.sub.3                                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      C.sub.2 H.sub.5                                                                     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     5-NO.sub.2                                                                          H   CH.sub.3                                                                          OCH.sub.3                                                                         CH.sub.3                                                                             N                                   SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      H     H     6-Br                                                                              H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         Cl     CH                                  SO.sub.2 N(CH.sub.2 CH.sub.3).sub.2                                                      C.sub.2 H.sub.5                                                                     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR65## H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                   ##STR66## H     H     H   H   CH.sub.3                                                                          H      CH                                   ##STR67## H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                    ##STR68## H     H     H   H   CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                    N                                    ##STR69## i-C.sub.3 H.sub.7                                                                   H     5-Br                                                                              H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                    ##STR70## H     7-F   H   H   OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                     N                                    ##STR71## H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                            6-F   H   CH.sub.3                                                                          CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                    N                                   C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   i-C.sub.3 H.sub.7                                                                        SO.sub.2 C.sub.6 H.sub.5                                                            H     H   H   CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                     CH                                  CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                            7-NO.sub.2                                                                          H   H   OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                      N                                   CO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          OCH.sub.3                                                                            CH                                  CO.sub.2 CH.sub.3                                                                        H     H     H   H   CH.sub.3                                                                          CH.sub.3                                                                             CH                                  CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CO.sub.2 CH.sub.3                                                                        H     5-OCH.sub.3                                                                         H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             N                                   CO.sub.2 CH.sub.3                                                                        H     H     H   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                             N                                   CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   CH.sub.3                                                                          CH.sub.3                                                                          CH.sub.3                                                                             N                                   CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            6-C.sub.2 H.sub.5                                                                   H   H   CH.sub.3                                                                          OCH.sub.3                                                                            N                                   CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            N                                   CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         OCH.sub.3                                                                            CH                                  CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                            H     H   H   OCH.sub.3                                                                         CH.sub.3                                                                             CH  200-203°(d)              CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         Cl     CH                                  CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                    CH                                  CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                      CH                                  CO.sub.2 CH.sub.3                                                                        H     H     H   H   OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                     N                                   __________________________________________________________________________

                                      TABLE II                                    __________________________________________________________________________     ##STR72##                                                                    R          R.sub.2                                                                            R.sub.3                                                                              R.sub.4                                                                          R.sub.5                                                                          X   Y     Z  m.p.(°C.)                    __________________________________________________________________________    H          H    4-F    H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                      H          H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     H          H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      H          H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     H          H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     H          H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      H          CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub. 3                                                                          CH                                     H          CH.sub.3                                                                           5-Cl   H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      H          CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      H          CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     H          CH.sub.3                                                                           H      4-Br                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      H          CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     H          C.sub.2 H.sub.5                                                                    H      H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                      H          i-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    CH                                     H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     H          SO.sub.2 C.sub.6 H.sub.5                                                           6-NO.sub.2                                                                           H  H  OCH.sub.3                                                                         Cl    CH                                     H          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                     CH.sub.3   H    H      5-Br                                                                             H  OCH.sub. 3                                                                        OCH.sub.3                                                                           CH                                     CH.sub.3   H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.3   H    6-CH.sub.3                                                                           H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  N                                      CH.sub.3   H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.3   H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.3   H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.3   H    6-C.sub.3 H.sub.7                                                                    H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.3   CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.3   CH.sub.3                                                                           H      H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.3   CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.3   CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.3   CH.sub.3                                                                           5-OC.sub.3 H.sub.7                                                                   H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.3   CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.3   C.sub.2 H.sub.5                                                                    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.3   n-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.3   C.sub.2 H.sub.5                                                                    4-Br   H  H  CH.sub.3                                                                          H     CH                                     CH.sub.3   CH.sub.3                                                                           4-Cl   6-Cl                                                                             H  CH.sub.3                                                                          Cl    CH                                     CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           H      H  CH.sub.3                                                                         CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     N                                      CH.sub.3   SO.sub.2 C.sub.6 H.sub.5                                                           5-NO.sub.2                                                                           H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      C.sub.2 H.sub.5                                                                          H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      C.sub.2 H.sub.5                                                                          H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     C.sub.2 H.sub.5                                                                          H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                    4-OCH.sub.3                                                                          H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    CH                                     C.sub.2 H.sub.5                                                                          C.sub.2 H.sub.5                                                                    H      H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     C.sub.2 H.sub.5                                                                          i-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   N                                      C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      C.sub.2 H.sub.5                                                                          SO.sub.2 C.sub.6 H.sub.5                                                           H      5-Cl                                                                             H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      n-C.sub.3 H.sub.7                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      n-C.sub.3 H.sub.7                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     n-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  CH                                     n-C.sub.3 H.sub.7                                                                        C.sub.3 H.sub.7                                                                    6-F    H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     n-C.sub.3 H.sub.7                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     n-C.sub.3 H.sub.7                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                     i-C.sub.3 H.sub.7                                                                        H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                     N                                      i-C.sub. 3 H.sub.7                                                                       H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      i-C.sub.3 H.sub.7                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      i-C.sub.3 H.sub.7                                                                        CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      n-C.sub.3 H.sub.7                                                                        H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     n-C.sub.3 H.sub.7                                                                        H    H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                     n-C.sub.3 H.sub.7                                                                        H    5-Br   7-Br                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     n-C.sub.3 H.sub.7                                                                        i-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     n-C.sub.4 H.sub.9                                                                        H    H      H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    N                                      n-C.sub.4 H.sub.9                                                                        H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      n-C.sub.4 H.sub.9                                                                        C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      s-C.sub.4 H.sub.9                                                                        H    H      H  H  OCH.sub.3                                                                         Cl    CH                                     s-C.sub.4 H.sub.9                                                                        H    6-OC.sub.2 H.sub.5                                                                   H  CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     s-C.sub.4 H.sub.9                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     t-C.sub.4 H.sub.9                                                                        H    H      H  H  OCH.sub.3                                                                         H     CH                                     t-C.sub.4 H.sub.9                                                                        CH.sub.3                                                                           H      4-Cl                                                                             H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      t-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      i-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  N                                      n-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      s-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     t-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     i-C.sub.4 H.sub.9                                                                        SO.sub.2 C.sub.6 H.sub.5                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               H    6-OCH.sub.3                                                                          H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 CH.sub.3                                                               CH.sub.3                                                                           5-Me   H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               C.sub.2 H.sub.5                                                                    H      7-Cl                                                                             CH.sub.3                                                                         OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                               C.sub.2 H.sub.5                                                                    H      H  H  CH.sub.3                                                                          Cl    CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                                .sub.-i-C.sub.3 H.sub.7                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 CH.sub.3                                                                -n-C.sub.3 H.sub.7                                                                7-F    H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                        H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                        C.sub.2 H.sub.5                                                                    H      6-Br                                                                             CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 C.sub.2 H.sub.5                                                        C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                H    H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH                                     CH.sub.2 CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                H    4-NO.sub.2                                                                           H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                     CH.sub.2 CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          H     CH                                     CH.sub.2 CO.sub.2 n-C.sub.3 H.sub.7                                                      H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 n-C.sub.3 H.sub.7                                                      H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 H                                                                      H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 H                                                                      H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 H                                                                      H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 H                                                                      H    6-OC.sub.2 H.sub.5                                                                   H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 H                                                                      H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 CO.sub.2 H                                                                      H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 CO.sub.2 H                                                                      CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 H                                                                      CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 CO.sub.2 H                                                                      CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 CO.sub.2 H                                                                      C.sub.2 H.sub.5                                                                    7-NO.sub.2                                                                           H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 CH.sub.3                                                                        H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CO.sub.2 CH.sub.3                                                                        H    7-Br   6-Br                                                                             H  CH.sub.3                                                                          Cl    CH                                     CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                           H      H  CH.sub.3                                                                         CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH                                     CO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CO.sub.2 CH.sub.3                                                                        C.sub.2 H.sub.5                                                                    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CO.sub.2 CH.sub.3                                                                        i-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         H     CH                                     CO.sub.2 C.sub.2 H.sub.5                                                                 H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 C.sub.2 H.sub.5                                                                 H    4-C.sub. 2 H.sub.5                                                                   H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  CH                                     CO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CO.sub.2 C.sub.2 H.sub.5                                                                 CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CO.sub.2 C.sub.2 H.sub.5                                                                 n-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         H    H      H  H  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                     N                                      CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         H    H      5-Cl                                                                             H  OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    N                                      CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         H    7-OCH.sub.3                                                                          H  H  OCH.sub.3                                                                         Cl    CH                                     CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          H     CH                                     CO.sub.2 .sub.-i-C.sub.3 H.sub.7                                                         CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   N                                      CO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CO.sub.2 -n-C.sub.3 H.sub.7                                                              C.sub.2 H.sub.5                                                                    6-Cl   H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CO.sub.2 -n-C.sub.3 H.sub.7                                                              n-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CO.sub.2 H H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CO.sub.2 H H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     CO.sub.2 H H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CO.sub.2 H H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CO.sub.2 H H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          Cl    CH                                     CO.sub.2 H C.sub.2 H.sub.5                                                                    H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH                                     CO.sub.2 H i-C.sub.3 H.sub.7                                                                  6-Cl   H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CO.sub.2 H n-C.sub. 3 H.sub.7                                                                 H      5-Br                                                                             H  CH.sub.3                                                                          H     CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    7-NO.sub.2                                                                           H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      6-Cl                                                                             CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       C.sub.2 H.sub.5                                                                    H      H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         Cl    CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       C.sub.2 H.sub.5                                                                    7-Cl   H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      (CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                       C.sub.3 H.sub.7                                                                    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      (CH.sub.2).sub.2 CO.sub.2 i-C.sub.3 H.sub.7                                              H    H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     N                                      (CH.sub.2).sub.2 CO.sub.2 i-C.sub.3 H.sub.7                                              H    H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH                                     (CH.sub.2).sub.2 CO.sub.2 i-C.sub.3 H.sub.7                                              H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     (CH.sub.2).sub.2 CO.sub.2 i-C.sub.3 H.sub.7                                              H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     (CH.sub. 2).sub.2 CO.sub.2 -n-C.sub.3 H.sub.7                                            H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    CH                                     (CH.sub.2).sub.2 CO.sub.2 -n-C.sub.3 H.sub.7                                             H    5-F    H  H  OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    N                                      (CH.sub.2).sub.2 CO.sub.2 -n-C.sub.3 H.sub.7                                             i-C.sub.3 H.sub.7                                                                  H      6-Br                                                                             H  OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   N                                      (CH.sub.2).sub.2 CO.sub.2 -n-C.sub.3 H.sub.7                                             CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 H                                                              H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      (CH.sub.2).sub.2 CO.sub.2 H                                                              H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     (CH.sub.2).sub.2 CO.sub.2 H                                                              H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     (CH.sub.2).sub.2 CO.sub.2 H                                                              H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 H                                                              H    6-Br   H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      (CH.sub.2).sub.2 CO.sub.2 H                                                              CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      (CH.sub. 2).sub.2 CO.sub.2 H                                                             n-C.sub.3 H.sub.7                                                                  H      H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      H  H  OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                H    H      5-Br                                                                             H  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                     N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         H     N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  N                                      CH.sub.2 OC.sub.2 H.sub.5                                                                i-C.sub.3 H.sub.7                                                                  7-iC.sub.3 H.sub.7                                                                   H  H  CH.sub.3                                                                          Cl    CH                                     CH.sub.2 OCH.sub.3                                                                       H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 OCH.sub.3                                                                       H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.2 OCH.sub.3                                                                       H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            N                                      CH.sub.2 OCH.sub.3                                                                       H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CH.sub.2 OCH.sub.3                                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 OCH.sub.3                                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 OCH.sub.3                                                                       H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 OCH.sub.3                                                                       C.sub.2 H.sub.5                                                                    4-Oi-C.sub.3 H.sub.7                                                                 H  H  OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    N                                      CH.sub.2 OCH.sub.3                                                                       C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CHO        H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CHO        H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CHO        H    H      H  H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     CHO        H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CHO        H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  CH                                     CHO        CH.sub.3                                                                           H      7-Cl                                                                             H  OCH.sub.3                                                                         Cl    CH                                     CHO        CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CHO        CH.sub.3                                                                           5-OCH.sub.3                                                                          H  H  OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   CH                                     SO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     SO.sub.2 CH.sub.3                                                                        H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      SO.sub.2 CH.sub.3                                                                        H    5-C.sub.2 H.sub.5                                                                    H  H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    N                                      SO.sub.2 CH.sub.3                                                                        H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          Cl    CH                                     SO.sub.2 CH.sub.3                                                                        CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH                                     SO.sub.2 CH.sub.3                                                                        i-C.sub.3 H.sub.7                                                                  H      7-Br                                                                             H  CH.sub.3                                                                          H     CH                                     SO.sub.2 C.sub.2 H.sub.5                                                                 i-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 C.sub.2 H.sub.5                                                                 i-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 C.sub.2 H.sub.5                                                                 i-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 C.sub.2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  N                                      SO.sub.2 C.sub.2 H.sub.5                                                                 C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      SO.sub.2 i-C.sub.3 H.sub.7                                                               H    H      H  CH.sub.3                                                                         CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   N                                      SO.sub.2 i-C.sub.3 H.sub.7                                                               H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 i-C.sub.3 H.sub.7                                                               H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 i-C.sub.3 H.sub.7                                                               n-C.sub.3 H.sub.7                                                                  5-OCH.sub.3                                                                          H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  CH.sub.3                                                                          C.sub.2 H.sub.5                                                                     N                                      SO.sub.2 -n-C.sub.3 H.sub.7                                                              H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 -n-C.sub.3 H.sub.7                                                              CH.sub.3                                                                           H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         CH.sub.2 OCH.sub.3                                                                  CH                                     SO.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     SO.sub.2 N(CH.sub. 3).sub.2                                                              H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                           H      H  CH.sub.3                                                                         CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                           H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3).sub.2                                                               i-C.sub.3 H.sub.7                                                                  4-CH.sub.3                                                                           H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3).sub.2                                                               C.sub.2 H.sub.5                                                                    6-Cl   4-Cl                                                                             H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   N                                      SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H    H      H  H  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                     N                                      SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      C.sub.2 H.sub.5                                                                    7-OiC.sub.3 H.sub.7                                                                  H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     SO.sub.2 N(CH.sub.3)C.sub.2 H.sub.5                                                      n-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          N(CH.sub.3).sub.2                                                                   CH                                     SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            N                                      SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        H    H      H  H  OCH.sub.3                                                                         H     N                                      SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                     N                                      SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        CH.sub.3                                                                           H      5-Br                                                                             H  CH.sub.3                                                                          OC.sub.2 H.sub.5                                                                    N                                      SO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                        CH.sub.3                                                                           4-CH.sub.3                                                                           H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7                                                      H    H      H  H  CH.sub.3                                                                          CH.sub.2 OCH.sub.3                                                                  N                                      SO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7                                                      H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7                                                      H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      SO.sub. 2 N(CH.sub.3)C.sub.3 H.sub.7                                                     H    H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 N(CH.sub.3)C.sub.3 H.sub.7                                                      n-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         Cl    CH                                     SO.sub.2 N(CH.sub.3) .sub.-i-C.sub.3 H.sub.7                                             n-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         CH.sub.3                                                                            CH                                     SO.sub.2 N(CH.sub.3) .sub.-i-C.sub.3 H.sub.7                                             n-C.sub.3 H.sub.7                                                                  H      7-Cl                                                                             H  CH.sub.3                                                                          CH.sub.3                                                                            CH                                     SO.sub.2 N(CH.sub.3) .sub.-i-C.sub.3 H.sub.7                                             n-C.sub.3 H.sub.7                                                                  H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      SO.sub.2 N(CH.sub.3) .sub.-i-C.sub.3 H.sub.7                                             C.sub.2 H.sub.5                                                                    5-NO.sub.2                                                                           H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           N                                      CH.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  CH.sub.3                                                                          OCH.sub.3                                                                           CH                                     CH.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           CH                                     CH.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  H  OCH.sub.3                                                                         OCH.sub.3                                                                           N                                      CH.sub.2 N(CH.sub.3 ).sub.2                                                              H    H      H  H  OCH.sub.3                                                                         N(CH.sub.3).sub.2                                                                   N                                      CH.sub.2 N(CH.sub.3).sub.2                                                               H    H      H  CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 N(CH.sub.3).sub.2                                                               CH.sub.3                                                                           H      H  CH.sub.3                                                                         OCH.sub.3                                                                         CH.sub.3                                                                            N                                      CH.sub.2 N(CH.sub.3).sub.2                                                               C.sub.2 H.sub.5                                                                    H      H  H  OCH.sub.3                                                                         Cl    CH                                     CH.sub.2 N(CH.sub.3).sub.2                                                               i-C.sub.3 H.sub.7                                                                  H      H  H  OCH.sub.3                                                                         OC.sub.2 H.sub.5                                                                    CH                                     __________________________________________________________________________

FORMULATIONS

Useful formulations of the compounds of Formula I can be prepared inconventional ways. They include dusts, granules, pellets, solutions,suspensions, emulsions, wettable powders, emulsifiable concentrates andthe like. Many of these may be applied directly. Sprayable formulationscan be extended in suitable media and used at spray volumes of from afew liters to several hundred liters per hectare. High strengthcompositions are primarily used as intermediates for furtherformulation. The formulations, broadly, contain about 0.1% to 99% byweight of active ingredient (s) and at least one of (a) about 0.1% to20% surfactant (s) and (b) about 1% to 99.9% solid or liquid diluent(s). More specifically, they will contain these ingredients in thefollowing approximate proportions:

                  TABLE 3                                                         ______________________________________                                                    Active  Weight Percent*                                                       Ingredient                                                                            Diluent(s)                                                                              Surfactant(s)                                   ______________________________________                                        Wettable Powders                                                                            20-90      0-74     1-10                                        Oil Suspensions,                                                                             3-50     40-95     0-15                                        Emulsions, Solutions,                                                         (including Emulsifiable                                                       Concentrates)                                                                 Aqueous Suspension                                                                          10-50     40-84     1-20                                        Dusts          1-25     70-99     0-5                                         Granules and Pellets                                                                        0.1-95      5-99.9  0-15                                        High Strength 90-99      0-10     0-2                                         Compositions                                                                  ______________________________________                                         *Active ingredient plus at least one of a Surfactant or a Diluent equals      100 weight percent.                                                      

Lower or higher levels of active ingredient can, of course, be presentdepending on the intended use and the physical properties of thecompound. Higher ratios of surfactant to active ingredient are sometimesdesirable, and are achieved by incorporation into the formulation or bytank mixing.

Typical solid diluents are described in Watkins, et al., "Handbook ofInsecticide Dust Diluents and Carriers", 2nd Ed., Dorland Books,Caldwell, N.J., but other solids, either mined or manufactured, may beused. The more absorptive diluents are preferred for wettable powdersand the denser ones for dusts. Typical liquid diluents and solvents aredescribed in Marsden, "Solvents Guide," 2nd Ed., Interscience, New York,1950. Solubility under 0.1% is preferred for suspension concentrates;solution concentrates are preferably stable against phase separation at0° C. "McCutcheon's Detergents and Emulsifiers Annual", MC PublishingCorp., Ridgewood, N.J., as well as Sisely and Wood, "Encyclopedia ofSurface Active Agents", Chemical Publishing Co., Inc., New York, 1964,list surfactants and recommended uses. All formulations can containminor amounts of additives to reduce foaming, caking, corrosion,microbiological growth, etc.

The methods of making such compositions are well known. Solutions areprepared by simply mixing the ingredients. Fine solid compositions aremade by blending and, usually, grinding as in a hammer or fluid energymill. Suspensions are prepared by wet milling (see, for example,Littler, U.S. Pat. No. 3,060,084). Granules and pellets may be made byspraying the active material upon preformed granular carriers or byagglomeration techniques. See J. E. Browning, "Agglomeration", ChemicalEngineering, Dec. 4, 1967, pp. 147ff. and "Perry's Chemical Engineer'sHandbook", 5th Ed., McGraw-Hill, New York, 1973, pp. 8-57ff.

For further information regarding the art of formulation, see forexample:

H. M. Loux, U.S. Pat. No. 3,235,361, Feb. 15, 1966, Col. 6, line 16through Col. 7, line 19 and Examples 10 through 41;

R. W. Luckenbaugh, U.S. Pat. No. 3,309,192, Mar. 14, 1967, Col. 5, line43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58,132, 138-140, 162-164, 166, 167 and 169-182;

H. Gysin and E. Knusli, U.S. Pat. No. 2,891,855, June 23, 1959, Col. 3,line 66 through Col. 5, line 17 and Examples 1-4;

G. C. Klingman, "Weed Control as a Science", John Wiley & Sons, Inc.,New York, 1961, pp. 81-96; and

J. D. Fryer and S. A. Evans, "Weed Control Handbook", 5th Ed., BlackwellScientific Publications, Oxford, 1968, pp. 101-103.

In the following examples, all parts are by weight unless otherwiseindicated.

EXAMPLE 8

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        3-[[(4-methoxy-6-methylpyrimidin-2-yl)aminocarbonyl]-                                                      80%                                              aminosulfonyl]-1-methyl-1H--indole-                                           2-carboxylic acid, methyl ester                                               sodium alkylnaphthalenesulfonate                                                                            2%                                              sodium ligninsulfonate        2%                                              synthetic amorphous silica    3%                                              kaolinite                    13%                                              ______________________________________                                    

The ingredients are blended, hammer-milled until all the solids areessentially under 50 microns, reblended, and packaged.

EXAMPLE 9

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        3-[[(4,6-dimethyl-1,3,5-triazin-2-yl)-                                                                 50%                                                  aminocarbonyl]-aminosulfonyl]-1-methyl-                                       1H--indole-2-carboxylic acid, methyl ester                                    sodium alkylnaphthalenesulfonate                                                                        2%                                                  low viscosity methyl cellulose                                                                          2%                                                  diatomaceous earth       46%                                                  ______________________________________                                    

The ingredients are blended, coarsely hammer-milled and then air-milledto produce particles essentially all below 10 microns in diameter. Theproduct is reblended before packaging.

EXAMPLE 10

    ______________________________________                                        Granule                                                                       ______________________________________                                        Wettable Powder of Example 9                                                                          5%                                                    attapulgite granules   95%                                                    (U.S.S. 20-40 mesh; 0.84-0.42 mm)                                             ______________________________________                                    

A slurry of wettable powder containing 25% solids is sprayed on thesurface of attapulgite granules in a double-cone blender. The granulesare dried and packaged.

EXAMPLE 11

    ______________________________________                                        Extruded Pellet                                                               ______________________________________                                        3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                                 25%                                                 aminocarbonyl]aminosulfonyl]-1-methyl-1H--                                    indole-2-carboxylic acid, methyl ester                                        anhydrous sodium sulfate  10%                                                 crude calcium ligninsulfonate                                                                            5%                                                 sodium alkylnaphthalenesulfonate                                                                         1%                                                 calcium/magnesium bentonite                                                                             59%                                                 ______________________________________                                    

The ingredients are blended, hammer-milled and then moistened with about12% water. The mixture is extruded as cylinders about 3 mm diameterwhich are cut to produce pellets about 3 mm long. These may be useddirectly after drying, or the dried pellets may be crushed to pass aU.S.S. No. 20 sieve (0.84 mm openings). The granules held on a U.S.S.No. 40 sieve (0.42 mm openings) may be packaged for use and the finesrecycled.

EXAMPLE 12

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        3-[[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-                                                          25%                                               aminosulfonyl]-1-methyl-1H--indole-2-                                         carboxylic acid, methyl ester                                                 polyoxyethylene sorbitol hexaoleate                                                                        5%                                               highly aliphatic hydrocarbon oil                                                                          70%                                               ______________________________________                                    

The ingredients are ground together in a sand mill until the solidparticles have been reduced to under about 5 microns. The resultingthick suspension may be applied directly, but preferably after beingextended with oils or emulsified in water.

EXAMPLE 13

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        N--[(4,6-dimethoxypyrimidin-2-yl)-                                                                   20%                                                    aminocarbonyl]-3-methyl-1H--indole-                                           2-sulfonamide                                                                 sodium alkylnaphthalenesulfonate                                                                      4%                                                    sodium ligninsulfonate  4%                                                    low viscosity methyl cellulose                                                                        3%                                                    attapulgite            69%                                                    ______________________________________                                    

The ingredients are thoroughly blended. After grinding in a hammer-millto produce particles essentially all below 100 microns, the material isreblended and sifted through a U.S.S. No. 50 sieve (0.3 mm opening) andpackaged.

EXAMPLE 14

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        N--[(4-methyl-6-methoxypyrimidin-2-                                                                  1%                                                     yl)aminocarbonyl]-3-methyl-1H--                                               indole-2-sulfonamide                                                          N,N--dimethylformamide 9%                                                     attapulgite granules   90%                                                    (U.S.S. 20-40 sieve)                                                          ______________________________________                                    

The active ingredient is dissolved in the solvent and the solution issprayed upon dedusted granules in a double cone blender. After sprayingof the solution has been completed, the blender is allowed to run for ashort period and then the granules are packaged.

EXAMPLE 15

    ______________________________________                                        Aqueous Suspension                                                            ______________________________________                                        N--[(4,6-dimethylpyrimidin-2-yl)-                                                                     40%                                                   aminocarbonyl]-3-methyl-1H--                                                  indole-2-sulfonamide                                                          polyacrylic acid thickener                                                                            0.3%                                                  dodecylphenol polyethylene glycol ether                                                               0.5%                                                  disodium phosphate       1%                                                   monosodium phosphate    0.5%                                                  polyvinyl alcohol       1.0%                                                  water                   56.7%                                                 ______________________________________                                    

The ingredients are blended and ground together in a sand mill toproduce particles essentially all under 5 microns in size.

EXAMPLE 16

    ______________________________________                                        Solution                                                                      ______________________________________                                        N--[(4-methyl-6-methoxy-1,3,5-triazin-                                                                  5%                                                  2-yl)aminocarbonyl]-3-methyl-1H--indole-                                      2-sulfonamide, sodium salt                                                    water                    95%                                                  ______________________________________                                    

The salt is added directly to the water with stirring to produce thesolution, which may then be packaged for use.

EXAMPLE 17

    ______________________________________                                        Low Strength Granule                                                          ______________________________________                                        N--[(4,6-dimethoxy-1,3,5-triazin-2-yl)-                                                               0.1%                                                  aminocarbonyl]-3-methyl-1H--indole-                                           2-sulfonamide                                                                 attapulgite granules   99.9%                                                  (U.S.S. 20-40 mesh)                                                           ______________________________________                                    

The active ingredient is dissolved in a solvent and the solution issprayed upon dedusted granules in a double-cone blender. After sprayingof the solution has been completed, the material is warmed to evaporatethe solvent. The material is allowed to cool and then packaged.

EXAMPLE 18

    ______________________________________                                        Granule                                                                       ______________________________________                                        3-[[(4-methoxy-6-methylpyrimidin-2-yl)                                                                 80%                                                  aminocarbonyl]aminosulfonyl]-1-methyl-                                        1H--indole-2-carboxylic acid, methyl ester                                    wetting agent             1%                                                  crude ligninsulfonate salt (containing                                                                 10%                                                  5-20% of the natural sugars)                                                  attapulgite clay          9%                                                  ______________________________________                                    

The ingredients are blended and milled to pass through a 100 meshscreen. This material is then added to a fluid bed granulator, the airflow is adjusted to gently fluidize the material, and a fine spray ofwater is sprayed onto the fluidized material. The fluidization andspraying are continued until granules of the desired size range aremade. The spraying is stopped, but fluidization is continued, optionallywith heat, until the water content is reduced to the desired level,generally less than 1%. The material is then discharged, screened to thedesired size range, generally 14-100 mesh (1410-149 microns), andpackaged for use.

EXAMPLE 19

    ______________________________________                                        High Strength Concentrate                                                     ______________________________________                                        3-[[(4,6-dimethylpyrimidin-2-yl)amino-                                                               99%                                                    carbonyl]aminosulfonyl]-1-methyl-1H--                                         indole-2-carboxylic acid, methyl ester                                        silica aerogel         0.5%                                                   synthetic amorphous silica                                                                           0.5%                                                   ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produce amaterial essentially all passing a U.S.S. No. 50 screen (0.3 mmopening). The concentrate may be formulated further if necessary.

EXAMPLE 20

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        3-[[(4,6-dimethylpyrimidin-2-yl)amino-                                                                   90%                                                carbonyl]aminosulfonyl]-1-methyl-1H--indole-2-                                carboxylic acid, methyl ester                                                 dioctyl sodium sulfosuccinate                                                                            0.1%                                               synthetic fine silica      9.9%                                               ______________________________________                                    

The ingredients are blended and ground in a hammer-mill to produceparticles essentially all below 100 microns. The material is siftedthrough a U.S.S. No. 50 screen and then packaged.

EXAMPLE 21

    ______________________________________                                        Wettable Powder                                                               ______________________________________                                        3-[[(4-methyl-6-methoxy-1,3,5-triazin-2-yl)-                                                           40%                                                  aminocarbonyl]-aminosulfonyl]-1-methyl-                                       1H--indole-2-carboxylic acid, methyl ester                                    sodium ligninsulfonate   20%                                                  montmorillonite clay     40%                                                  ______________________________________                                    

The ingredients are thoroughly blended, coarsely hammer-milled and thenair-milled to produce particles essentially all below 10 microns insize. The material is reblended and then packaged.

EXAMPLE 22

    ______________________________________                                        Oil Suspension                                                                ______________________________________                                        N--[(4,6-dimethoxy-1,3,5-triazin-2-yl-                                                               35%                                                    aminocarbonyl]-3-methyl-1H--indole-                                           2-sulfonamide                                                                 blend of polyalcohol carboxylic                                                                       6%                                                    esters and oil soluble petroleum                                              sulfonates                                                                    xylene                 59%                                                    ______________________________________                                    

The ingredients are combined and ground together in a sand mill toproduce particles essentially all below 5 microns. The product can beused directly, extended with oils, or emulsified in water.

UTILITY

The compounds of the present invention are active herbicides. They haveutility for broad-spectrum pre-and/or post-emergence weed control inareas where complete control of all vegetation is desired, such asaround fuel storage tanks, ammunition depots, industrial storage areas,parking lots, drive-in theaters, around billboards, highway and railroadstructures. Alternatively, the subject compounds are useful for theselective weed control in crops, such as wheat, cotton and soybeans.

The rates of application for the compounds of the invention aredetermined by a number of factors, including their use as selective orgeneral herbicides, the crop species involved, the types of weeds to becontrolled, weather and climate, formulations selected, mode ofapplication, amount of foliage present, etc. In general terms, thesubject compounds should be applied at levels of around 0.03 to 10kg/ha, the lower rates being suggested for use on lighter soils and/orthose having a low organic matter content, for selective weed control orfor situations where only short-term persistence is required.

The compounds of the invention may be used in combination with any othercommercial herbicide examples of which are those of the triazine,triazole, uracil, urea, amide, diphenylether, carbamate and bipyridyliumtypes.

The activity of these compounds was discovered in greenhouse tests. Thetests are described and the data resulting from them are shown below.

TEST A

Seeds of crabgrass (Digitaria spp.), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), cassia (Cassia tora), morningglory(Ipomoea sp.), cocklebur (Xanthium sp.), sorghum, corn, soybean, rice,wheat and nutsedge tubers (Cyperus rotundus) were planted in a growthmedium and treated pre-emergence with the chemicals dissolved in a nonphytotoxic solvent solution of the compounds of Table A. At the sametime, cotton having five leaves (including cotyledonary ones), bushbeans with the third trifoliate leaf expanding, crabgrass, barnyardgrassand wild oats with two leaves, cassia with three leaves (includingcotyledonary ones), morningglory and cocklebur with four leaves(including the cotyledonary ones), sorghum and corn with four leaves,soybean with two cotyledonary leaves, rice with three leaves, wheat withone leaf, and nutsedge with three to five leaves were sprayed with anon-phytotoxic solvent solution of the compounds of Table A. Treatedplants and controls were maintained in a greenhouse for sixteen days,whereupon all species were compared to controls and visually rated forresponse to treatment. The ratings for the compounds tested by thisprocedure are presented in Table A. It will be seen the compounds testedpossess high herbicidal activity and that certain compounds are usefulfor weed control in wheat and soybeans. The ratings are based on anumerical scale extending from 0=no injury, to 10=complete kill. Theaccompanying descriptive symbols have the following meanings:

G=growth retardation;

C=chlorosis/necrosis;

6Y=abscised buds or flowers;

U=unusual pigmentation;

E=emergence inhibition; and

H=formative effects

U=unusual pigmentation

P=terminal bud injury.

    TABLE A      POST-EMERGENCE           BARN-  MORN- COCK-     BUSH- COT- SOR-  SOY-     WILD  YARD- CRAB- ING- LE- CAS- NUT-  kg/ha BEAN TON GHUM CORN BEAN     WHEAT OATS RICE GRASS GRASS GLORY BUR SIA SEDGE      ##STR73##      0.4 6C,9G,6Y 6C,9G 9C 9C 9C 5C, 9H 5C,9H 2C, 9G 9C 2C,9G 2C, 4G 10C     6C,9G 1C, 8G      ##STR74##      0.4 6C,9G,6Y 5C,9G 4C, 9G 9C 6C,9G 5C, 9G 6C,9G 6C,9G 10C 5C,9G 10C 10C     9C 4C, 8G      ##STR75##      0.4 9C 9C 5C, 9G 9C 9C 5C, 9G 5C,9G 6C,9G 9C 6C, 9G 9C 6C, 9G 6C,9G 4C,     9G      ##STR76##      0.4 7C,9G,6Y 6C,9H 5C, 9G 3C,9G 9C 2C, 9G 2C,9G 6C,9G 5C, 9H 5C, 9G 6C,     9G 6C, 9G 9C 4C, 9G      ##STR77##      0.4 9C 9C 10C 2U,9H 6C,9G 2C, 9G 5C,9G 5C,9G 5C, 9H 5C, 9G 3C, 9G 9C    9     5C,G 2C, 9G      ##STR78##      0.4 9C 9C 9C 3C,8H 9C 3U, 9G 6C,9G 9C 5C, 9H 6C, 9G 9C 9C 9C 5C, 9G      ##STR79##      0.4 1B 1B 2B 2B 1B 1B 1B 1B 5B 2B 3B 2B 2B 0      ##STR80##      0.05 2C,2H 0 0 3G 1H,5G 0 0 1C,5G 0 0 1C 1C 1C 0      ##STR81##      0.05 4C,8G,6Y 2C,5G 4C, 9G 2C,9H 3C,8G 3C, 9H 2C,9H 5C,9G 3C, 8H 2C, 7G     2C, 6G 2C, 8G 3C 9G      ##STR82##      0.4 2C,3G 0 0 0 0 0 0 0 0 0 0 0 0 0       PRE-EMERGENCE         BARN-  MORN- COCK-           YARD- CRAB- ING-     LE- CAS- NUT-  kg/ha SORGHUM CORN SOYBEAN WHEAT WILD OATS RICE GRASS     GRASS GLORY BUR SIA SEDGE      ##STR83##      0.4 6C 10H 2C 2C 5C 10E 5C 5C 8G 9H 8H 10E      ##STR84##      0.4 5C, 9H 9G 9H 9H 4C, 9G 10E 6C, 9H 6C, 9G 9G 9H 8G 10E      ##STR85##      0.4 7C, 9H 9H 9H 9H 3C, 9G 10E 6C, 9G 4C, 9G 9G 9H 9G 9G      ##STR86##      0.4 5C, 9G 9G 3C, 8H 1C, 9G 4C, 9G 10E 5C, 9H 3C, 8G 9G 9H 9G 4C, 9G      ##STR87##      0.4 6C, 9H 2C,9G 3C, 9H 9H 6C, 9G 5C,9H 5C, 9H 3C, 3G 9G -- 8G 9G      ##STR88##      0.4 7C, 9H 2U,9G 8H 2C, 9G 5C, 9G 10E 5C, 9H 4C, 9G 9G 9H 2C,9G 10E      ##STR89##      0.4 2C 3G 3G 1C 1C 5G 6C 0 5G -- 2C 0      ##STR90##      0.05 2C, 7G 2C,6G 1H 3G 8G 2C,4G 3G 0 2H -- 1C 0      ##STR91##      0.05 2C, 9H 1C,9H 2C, 7H 1C, 9G 3C, 9G 5C,9H 4C, 8H 1C, 6G 1C, 4H 9H 4G     4G, 1C      ##STR92##      0.4 4G 1C,5G 0 1C, 6G 2C, 5G 3G 0 0 0 -- 0 0

TEST B

Two plastic bulb pans were filled with fertilized and limed Fallsingtonsilt loam soil. One pan was planted with corn, sorghum, Kentuckybluegrass and several grassy weeds. The other pan was planted withcotton, soybeans, purple nutsedge (Cyperus rotundus), and severalbroadleaf weeds. The following grassy and broadleaf weeds were planted:crabgrass (Digitaria sanguinalis), barnyardgrass (Echinochloacrusgalli), wild oats (Avena fatua), johnsongrass (Sorghum halepense),dallisgrass (Paspalum dilatatum), giant foxtail (Setaria faberii),cheatgrass (Bromus secalinus), mustard (Brassica arvensis), cocklebur(Xanthium pensylvanicum), pigweed (Amaranthus retroflexus), morningglory(Ipomoea hederacea), cassia (Cassia tora), teaweed (Sida spinosa),velvetleaf (Abutilon theophrasti), and jimsonweed (Datura stramonium). A12.5 cm diameter plastic pot was also filled with prepared soil andplanted with rice and wheat. Another 12.5 cm pot was planted withsugarbeets. The above four containers were treated pre-emergence withtwo of the test compounds within the scope of the invention.

Twenty-eight days after treatment, the plants were evaluated andvisually rated for response to the chemical treatments utilizing therating system described previously for Test A. The data are summarizedin Table B. Note that the compounds are useful for weed control in cropssuch as soybeans, wheat and cotton.

                  TABLE B                                                         ______________________________________                                        PRE-EMERGENCE ON FALLSINGTON SILT LOAM                                        ______________________________________                                         ##STR93##                                                                    Rate kg/ha        0.03       0.12                                             ______________________________________                                        Crabgrass         3G         6G                                               Barnyardgrass     3G         7G,3H                                            Sorghum           10C        10C                                              Wild Oats         7G, 3H     7G, 5H                                           Johnsongrass      4G, 2H     6G, 5H                                           Dallisgrass       0          4G                                               Giant foxtail     3G         5G, 3H                                           Ky. bluegrass     7G, 5H     8G, 5H                                           Cheatgrass        5G, 3H     8G, 8C                                           Sugarbeets        7G, 3C     7G, 7C                                           Corn              4G, 4U     6G, 5H                                           Mustard           7G, 5C     9G, 9C                                           Cocklebur         6G, 3H     8G, 5H                                           Pigweed           5G         10E                                              Nutsedge          0          7G, 2C                                           Cotton            0          3G                                               Morningglory      0          2G                                               Cassia            4G         4G                                               Teaweed           5G         6G                                               Velvetleaf        2G         8G, 5H                                           Jimsonweed        3G         6G, 6C                                           Soybean           0          3G                                               Rice              6G, 5H     8G, 8C                                           Wheat             4G         5G                                               ______________________________________                                         ##STR94##                                                                    Rate kg/ha        0.03       0.12                                             ______________________________________                                        Crabgrass         3G         4G                                               Barnyardgrass     6G         8G, 3H                                           Sorghum           8G, 5H     10C                                              Wild Oats         7G, 3H     7G, 3H                                           Johnsongrass      6G, 5H     7G, 5H                                           Dallisgrass       3G         5G                                               Giant foxtail     4G, 3H     7G, 3H                                           Ky. bluegrass     8G, 3H     8G, 8C                                           Cheatgrass        4G         8G, 3H                                           Sugarbeets        5G, 3C     7G, 7C                                           Corn              5G, 5H     6G, 5H                                           Mustard           7G, 8C     7G, 7C                                           Cocklebur         4G, 3H     5G, 3H                                           Pigweed           5G         8G, 8C                                           Nutsedge          0          3G                                               Cotton            0          3G                                               Morningglory      0          4G                                               Cassia            0          3G                                               Teaweed           6G, 2C     7G, 2C                                           Velvetleaf        5G, 5H     7G, 5H                                           Jimsonweed        3G         6G, 2C                                           Soybean           0          4G, 2C                                           Rice              8G, 5H     8G, 5H                                           Wheat             2C         3G, 3C                                           ______________________________________                                    

I claim:
 1. A compound selected from ##STR95## where R is H, C₁ -C₄ alkyl, (CH₂)_(m) CO₂ R₉, CH₂ OC₂ H₅, SO₂ R₁₀, CHO, SO₂ NR₁₁ R₁₂₋, CH₂ N(CH₃)₂ or CH₂ OCH₃ ;R₁ is H, C₁ -C₄ alkyl, CO₂ R₆, C(O)NR₇ R₈, C(O)R₁₀, SO₂ R₁₀, or SO₂ NR₁₁ R₁₂ ; R₂ is H, C₁ -C₃ alkyl or SO₂ C₆ H₅ ; R₃ is H, F, Cl, Br, C₁ -C₃ alkyl, C₁ -C₃ alkoxy or NO₂ ; R₄ is H, Cl or Br; R₅ is H or CH₃ ; R₆ is C₁ -C₄ alkyl, C₃ -C₄ alkenyl, CH₂ CH₂ Cl or CH₂ CH₂ OCH₃ ; R₇ and R₈ are independently H or C₁ -C₄ alkyl, provided that the total number of carbon atoms is less than or equal to 4; R₉ is H or C₁ -C₃ alkyl R₁₀ is C₁ -C₃ alkyl; R₁₁ and R₁₂ are independently C₁ -C₃ alkyl, provided that the total number of carbon atoms is less than or equal to
 4. m is 0, 1 or 2; A is ##STR96## X is CH₃ or OCH₃ ; Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃, Cl, H, C₂ H₅ or N(CH₃)₂ ; and Z is N;provided that (1) when R₂ is SO₂ C₆ H₅, then R₁ and R are H or C₁ -C₃ alkyl; and (2) when m is 0, then R₉ is C₁ -C₃ alkyl.
 2. A compound of claim 1, Formula I where R₁ is H, C₁ -C₃ alkyl, CO₂ R₆, C(O)NR₇ R₈, SO₂ NR₁₁ R₁₂ or SO₂ R₁₀ ; and R₅ is H.
 3. A compound of claim 2 where R₃ and R₄ are H.
 4. A compound of claim 3 where R₂ is H or CH₃.
 5. A compound of claim 4 where R₁ is H, CO₂ CH₃, SO₂ CH₃ or SO₂ N(CH₃)₂.
 6. A compound of claim 5 where Y is CH₃, OCH₃, OC₂ H₅, CH₂ OCH₃ or Cl.
 7. A compound of claim 1, Formula II where R is H, C₁ -C₃ alkyl, (CH₂)_(m) CO₂ R₉, SO₂ R₁₀ or SO₂ NR₁₁ R₁₂ ; and R₅ is H.
 8. A compound of claim 7 where R₃ and R₄ are H.
 9. A compound of claim 8 where R₂ is H or CH₃.
 10. A compound of claim 9 where R is H, CH₃ or (CH₂)_(m) CO₂ --(C₁ -C₃ alkyl).
 11. A compound of claim 10 where Y is CH₃, OCH₃, OC₂ H₅, or CH₂ OCH₃ .
 12. The compound of claim 1, 3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl) aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester.
 13. The compound of claim 1, 3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl) aminocarbonyl]aminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester.
 14. The compound of claim 1, 3-[[(4-methyl-6-methoxy-1,3,5-triazin-2-yl) aminocarbonyl]-aminosulfonyl]-1-methyl-1H-indole-2-carboxylic acid, methyl ester.
 15. The compound of claim 1, N-[(4,6-dimethoxy-1,3,5-triazin-2-yl) aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide.
 16. The compound of claim 1, N-[4,6-dimethoxy-1,3,5-triazin-2-yl) aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide.
 17. The compound of claim 1, N-[(4-methyl-6-methoxy-1,3,5-triazin-2-yl) aminocarbonyl]-3-methyl-1H-indole-2-sulfonamide.
 18. The compound of claim 1, 3-[[(4,6-dimethoxy-1,3,5-triazin-2-yl) aminocarbonyl]-aminosulfonyl]-1H-indole-2-carboxylic acid, ethyl ester.
 19. The compound of claim 1, 3-[[(4-methoxy-6-methyl-1,3,5-triazin-2-yl) aminocarbonyl]-aminosulfonyl]-1H-indole-2-carboxylic acid, ethyl ester.
 20. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 1 and at least one of the following: surfactant, solid or liquid diluent.
 21. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 2 and at least one of the following: surfactant, solid or liquid diluent.
 22. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 3 and at least one of the following: surfactant, solid or liquid diluent.
 23. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 4 and at least one of the following: surfactant, solid or liquid diluent.
 24. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 5 and at least one of the following: surfactant, solid or liquid diluent.
 25. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 6 and at least one of the following: surfactant, solid or liquid diluent.
 26. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 7 and at least one of the following: surfactant, solid or liquid diluent.
 27. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 8 and at least one of the following: surfactant, solid or liquid diluent.
 28. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 9 and at least one of the following: surfactant, solid or liquid diluent.
 29. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 10 and at least one of the following: surfactant, solid or liquid diluent.
 30. A composition suitable for controlling the growth of undesired vegetation which comprises an effective amount of a compound of claim 11 and at least one of the following: surfactant, solid or liquid diluent.
 31. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 1. 32. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 2. 33. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 3. 34. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 4. 35. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 5. 36. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 6. 37. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 7. 38. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 8. 39. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 9. 40. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 10. 41. A method for controlling the growth of undesired vegetation which comprises applying to the locus to be protected an effective amount of a compound of claim
 11. 